Sizing of textile filament and yarn with mixture of hydroxy polymer and hydrolyzed starch



United States Patent M SIZING 0F TEXTILE FILAMENT AND YARN WITH MIXTUREOF HYDROXY POLYMER AND HY- DROLYZED STARCH Donald D. Donermeyer,Springfield, and Robert A. Isaksen, East Longmeadow, Mass., assignors toMonsanto Company, St. Louis, Mo., a corporation of Delaware No Drawing.Filed Apr. 25, 1967, Ser. No. 633,367

Int. Cl. D06m 11/00 US. Cl. 117-l39.5 4 Claims ABSTRACT OF THEDISCLOSURE The application describes the sizing of textile filaments andyarns with a hydroxy-containing polymer system containing up to about 75weight percent of a non-crystalline starch hydrolyze having a dextroseequivalent of from about 13 to about 38. The sized filaments and yarnsexhibit improved processing and weaving efficiency.

BACKGROUND OF THE INVENTION This invention relates to the sizing oftextile filaments and yarns.

Many filaments and yarns both of natural and synthetic materials requirea protective coating to prevent breakage thereof during weaving andprocessing operations. The protective coatings are known as sizes andthe application of them to the filaments and yarns is known as sizing.The size must not only protect the filaments and yarns from snags,pulled threads and breakage but must also adhere so as not to accumulateon the weaving equipment. Moreover, the size must be capable of beingreadily removable prior to the dyeing of the woven fabric.Hydroxy-containing polymers, such as polyvinyl alcohol and relatedpolymers are desirable as textile sizes. However, such polymers are notentirely satisfactory sizes formers. Thus, much industrial elfort hasbeen expended in the modification of hydroxy-containing polymers toimprove their capability for use as sizes. Various additives have beenproposed for modifying hydroxy-containing polymers such as boric acid,metal salts, urea, starches and sugars. Such additives are notcompletely satisfactory in obtaining sizing compositions ofhydroxy-containing polymers because of incompatibility in eithersolution form or solid form or both. Also, either the expense of theadditives has made their use with hydroxy-containing polymerscommercially prohibitive or the additives have enhanced one property ofthe polymer at the sacrifice of another desirable property. Heretofore,again because of compatibility problems, the additives forhydroxy-containing polymers have been limited to low quantities ofaddition or low level of extension. It is, of course, desirable toextend hydroxy-containing polymers at high levels for economic reasons.

In the sizing of textile filaments and yarns, the size is applied from asolution and then dried to a solid thereby requiring compatibility ofthe additive with the hydroxycontaining polymer both in solution formand in solid form. Additives such as starch and low molecular weightsaccharides are dissolvable or dispersible in hot water but exhibitretrogradation with crystallization upon cooling. Thus, when suchmaterials are used as extenders for polyvinyl alcohol as a size, theretrogradation of the materials on cooling or during film formationyields twophase films having poor mechanical and physical properties.

SUMMARY This invention is directed to the sizing of textile filamentsand yarns with a particular hydroxyl-containing polymer size system andto improved filaments and yarns sized with such system.

Accordingly, typical objects of this invention are to provide (1)novelsized textile filaments and yarns, (2) sized textile filaments and yarnshaving a combination of improved processing properties, and (3) aprocess for sizing textile filaments and yarns.

Other objects, aspects and advantages of this invention will becomeapparent to those skilled in the art upon further study of thisdisclosure in the appended claims.

In accordance with this invention, an improved process for sizingtextile filaments and yarns is provided which comprises applying theretoa coating of a composition containing a water-soluble hydroxy-containingpolymer and 2575 weight percent, based on the weight of said polymer, ofa particular starch hydrolyzate. The improved textile filaments andyarns of this invention comprise said yarns sized with a compositioncomprising a water soluble hydroxy-containing polymer and 25-75 weightpercent based on the weight of said polymer of a particular starchhydrolyzate.

The particular starch hydrolyzates employed in the composition useful inthis invention are non-crystalline and can be formed from any starch.The corn starch derivatives are presently preferred because of theircommercial availability. The hydrolysis of corn starch to convert starchto dextrose is well known and is carried out by use of acid alone or byuse of acid intially followed by enzyme hydrolysis. However, theconversion reaction may be regulated to produce intermediatehydrolyzates containing various amounts of intermediate products in thechemical path from starch to dextrose. The characteristics of a porductas a hydrolyzate is expressed by a DB. number which is the ratio ofdextrose equivalent, or in other words, of reducing sugars, to the totaldry substance of the hydrolyzate. Completely hydrolyzed corn starch iscorn sugar or dextrose which has a 100 DE. The commercial intermediatehydrolyzates of corn starch are termed dextrins 13D.E.), malto-dextrins(13 to 28D.E.), and corn syrups (28 and higher DE). The corn syrups arefurther classed by degree of conversion, i.e. low (28 to 38D.E.),regular (38 to 48D.E.), intermediate (48 to 58D.E.), high (58 to 68D.E.)and extra high (68 and higher D.E.). Relative to colloidal starch, thehydrolyzates are non-colloidal compounds of small molecular size and areof such character that they may be dried to a powder. The starchhydrolyzates compatible with hydroxy-containing polymer compositionsuseful in this invention are those termed malto-dextrins and lowconversion corn syrups, i.e. having a DB ranging from about 13 to about38.

The hydroxy-containing polymers employed in the compositions useful inthis invention include the polymeric materials having a viscositydetermined from a 4% aqueous solution at 20 C. up to about 200centipoises and containing a plurality of recurring hydroxy groupseither in the form of the alcohol or partially esterified alcohol.

More specifically, one group of hydroxy-containing polymers employed inthe composition useful in this invention are the (A) water solublehomopolymers of vinyl esters which are from to and preferably from 87 to99% hydrolyzed; (B) water soluble hydrolyzed copolymers of at least 50weight percent of a vinyl ester and up to 50 weight percent of anethylenically unsaturated material copolymerizable therewith, such asethylene, propylene, acrylates, vinyl chloride, maleates, fumarates, andthe like or mixtures thereof; and (C) physical blends of (A) and (B).Examples of suitable hydroxy-containing polymers are polyvinyl alcohol,par- Corn Syrups and Sugars, 3rd ed., 1965, Corn Industries ResearchFoundation, Inc., p. 15.

tially hydrolyzed polyvinyl acetate, partially hydrolyzed polyvinylpropionate, partially hydrolyzed polyvinyl butyrate, partiallyhydrolyzed polyvinyl stearate, partially hydrolyzed polyvinyltrifluoroacetate, and the like; partially hydrolyzed copolymers of vinylacetate with ethylene, vinyl chloride, or acrylonitrile, and the like.Polyvinyl alcohol is the presently preferred polymer.

Other extenders and plasticizers for hydroxy-containing polymers, suchas boric acid, urea, glycerine, and the like, may be present incombination with the particular starch hydrolyzates set forth above inthe composition useful in this invention. When a combination ofextenders is employed, the particular starch hydrolyzates shouldcomprise at least about 60%, by weight, of the total quantity ofextenders employed which should not exceed about 75% by weight of thecomposition.

The polyhydroxy-containing polymers and particular starch hydrolyzatesuseful in this invention are combined by slurrying them in water andthen heating the slurry to dissolve the polymer and hydrolyzate. Wateris the preferred medium for dissolving the polymer and hydrolyzate toform the sizing solution, however, it is to be understood that anymedium capable of slurrying and/ or dissolving the polymer andhydrolyzate and useful in sizing applications can be equally employed.

The sizing of textile filaments and yarns is obtained in accordance withthis invention by applying to the filaments and yarns a solution,preferably aqueous solution of a water soluble hydroxy-containingpolymer and up to about 75 weight percent, preferably 25 to 75 weightpercent, of a starch hydrolyzate having a DB of from about 13 to about38, based on the weight of the polymer. Any quantity of polymer andhydrolyzate can be present in the solution, however, generally not morethan 25%, based upon solids, will be used and preferably only 2 to 10%need be used to obtain satisfactory results. The sizing solution isapplied to the filaments and/or yarns in amounts of 1-20 weight percentbased upon the weight of the filaments and/ or yarns. The application ofthe sizing solution to the textile filaments of yarns can beaccomplished in any suitable manner such as spraying, brushing,immersion, and the like. Preferably, the filaments or yarns are drawnthrough a bath of the sizing tolution, passed hmlgh squeeze rolls toremove excess) solution and tl/e'n dried.

The following examples are set forth to describe more fully the practiceof this invention and the particular materials, quantities andconditions described should not be considered as limitations upon theinventive concept and scope thereof disclosed herein. Where parts arementioned in this disclosure, they are parts by weight unless otherwisespecified.

EXAMPLE I Fifty-five parts of polyvinyl alcohol (89% hydrolyzed) and 45parts of corn starch hydrolyzate having a D.E. of 24 are slurried in 900parts of water. The polyvinyl alcohol and hydrolyzate are dissolved byheating the slurry at 85 C. for 15 minutes. The solution is designatedas textile sizing solution 1. A second solution, designated textilesizing solution 2, is prepared by dissolving sufiicient 89% hydrolyzedpolyvinyl alcohol in water to provide a 7% solids solution. A thirdsolution, designated textile sizing solution 3, is prepared bydissolving parts of 89% hydrolyzed polyvinyl alcohol, 130 parts ofstarch and 13 parts of an acrylic binder in 900 parts of water toprovide a 15% solids solution. To each of these solutions is added 5weight percent of a waxy lubricant.

Textile yarn (Warp 5,900 ends of 65/35 polyester/cotton yarn 50/1) issized separately with each of the sizing solutions prepared above and isprocessed on a commercial can slasher having an internal steam pressureof 35 pounds per square inch. The size box temperature is maintained at170 F. for solutions 1 and 2 and at 200 F. for solution 3, and thesqueeze roll is held at a total pressure of 1200 pounds. Each of theseparately sized warps is tested for slasher performance and weavingperformance.

The yarn sized with textile sizing solution 1, having an applied totalsolids of 13 /2 weight percent based on the weight of the yarn, iscleanly and easily separated at the split rods with little or noshedding and only a single leasing is required. At start up, breakage ofonly 1 Warp end occurs. The sizing solution in the size box remainshomogeneous throughout the operation and exhibits no tendency to form asurface skin. The sized yarn is subsequently woven on a commercial loom.The loom operates at a weaving elficiency of about with approximatelyonly 0.5 Warp stops per hour. (Warp stops result when a breakage of thesized yarn occurs.)

The same grade of Warp yarn sized with textile sizing solution 2, havingan applied total solids of 10 weight percent based on the weight of theyarn, is separated with difficulty at the split rods but with little orno shedding. At start up, breakage of 5 to 11 warp ends occur and adouble leasing is required. The sizing solution forms a surface skinduring intermittent operations and must be replaced to allow continuedoperation of the slasher. The sized yarn is subsequently woven on acommercial loom. The weaving efiiciency is about the same as that foryarn sized with solution 1. However, about 10% polyvinyl alcohol wasapplied to the yarn from solution 2, compared with 7% polyvinylalcoholapplied from solution 1.

The above described sequence of operations is repeated using textilesizing solution 3 except that the starch requires a cook period of atleast 1 hour to form the solution. The sizing solution exhibits similartendency to form a skin or film as that described in connection withsizing solution 2. The sized yarn, having an applied total solids of 22weight percent based on the weight of the yarn, is separated easily butexhibits excessive shedding. At start up, breakage of 5 to 10 Warp endsoccurs. Subsequent weaving of the sized yarn on a commercial loomexhibits a weaving efficiency of 93% With about 1.5 warp stops per hour.

This example clearly shows that the yarn sized in accordance with thisinvention, solution 1, performs much better than unmodified hydrolyzedpolyvinyl alcohol, solution 2, or a conventional size, solution 3, insolution compatibility, slashing, and weaving efliciency.

EXAMPLE II Nine pounds of polyvinyl alcohol (89% hydrolyzed), 8 poundsof corn starch hydrolyzate having a DB of 22, 1 pound of glycerine and 3pounds of a lubricant are slurried in gallons of water. The slurry isheated at 85 C. for 20 minutes and then the solution is stored at F.This solution is designated as sizing solution 1. A second solution isprepared in like manner using 18 pounds of polyvinyl alcohol (89%hydrolyzed) having a viscosity of 50 centipoises and 3 pounds of alubricant. A third solution is prepared in a like manner using 18 poundsof polyvinyl alcohol (89% hydrolyzed) having a viscosity of 5centipoises and 3 pounds of a lubricant. A fourth solution is preparedin a like manner using 24 pounds of gelatin, 6 pounds of a lubricant, 1pound of a penetrant and 100 gallons of water by heating at 850 C. for20 minutes.

Textile yarn (warp 3000 ends of /40/2 (denier/filaments/ turns per inch)(filament rayon) is sized separately with each of the sizing solutionsprepared above and is run on a commercial 9 can slasher having aninternal steam pressure of 30 psi. The size box temperature ismaintained at IDS-110 F. and the squeeze roll is held at a totalpressure of 1400 lbs. Each of the separately sized yarns is tested forslasher performance and Weaving performance.

The yarn sized with solution 1, having an applied total solids of 1.7weight percent based on the weight of the yarns, is cleanly and easilyseparated at the split rods with little or no shedding and only a singleleasing is required. The sizing solution in the size box remainshomogeneous throughout the operation and exhibits no tendency to form asurface skin. The yarn is subsequently woven on a commercial loom. Theloom operates at a weaving efficiency of about 94% with the result ofonly 3% fabric seconds.

The yarn sized with solution 2 is difficult to separate at the splitrods and causes severe yarn breakage. The sizing solution in the sizebox forms a surface skin which must be continually removed to allowoperation of the slasher. It is impossible to obtain yarn which isusable on the looms due to excess breakage of the yarn on the slasher.

The yarn sized with solution 3, having an applied total solids of 1.7weight percent based on the weight of the yarn, is separated withdifficulty at the split rods. The yarn is subsequently Woven on acommercial loom. The loom operates at a weaving efiiciency of about 93%with 4% fabric seconds.

The yarn sized with solution 4, having an applied total solids of 3.2weight percent is woven on a commercial loom at a weaving efficiency of94% with 3% fabric seconds. Although yarn sized with solution 4 gave thesame weaving efliciency as yarn sized in accordance with this invention,solution 1, almost twice the quantity of solution 4 size was applied tothe yarn to obtain such weaving efiiciency as was the quantity ofsolution 1 size.

This example clearly shows that the yarn sized in accordance with thisinvention, solution 1, performs much better than unmodified hydrolyzedpolyvinyl alcohols, solutions 2 and 3, or a conventional size, solutionfor, in solution compatibility, slashing, weaving efilciency and/orquantity of size required on the yarn. Also, the yarn sized withsolution 1 possesses finishing properties such as receptivity to dyessuperior to yarn sized with the conventional sizes.

Various modifications will be apparent to those skilled in the art fromthe preceding disclosure which may be made in or to the compositiondisclosed and which will not depart from the spirit and scope thereof.

What is claimed is:

1. Textile filaments and yarns containing a size of an admixturecomprising a water-soluble hydroxy-containing polymer and anon-crystalline starch hydrolyzate having a dextrose equivalent value offrom about 13 to about 38; said hydrolyzate comprising from about 25% toabout by weight based upon the weight of the water-solublehydroxy-containing polymer; the admixture of watersolublehydroxy-containing polymer and non-crystalline starch hydrolyzate beingpresent in an amount of from about 1% to about 20% solids by weightbased upon the weight of the filament and/ or yarn.

2. The article of claim 1 wherein said size comprises 2-10 weightpercent based on the weight of the filaments and yarns.

3. The article of claim 1 wherein said polymer is a vinyl esterhomopolymer which is 87-99% hydrolyzed and has a viscosity of up to 200centipoises determined at 20 C. from a 4% aqueous solution of saidpolymer.

4. The article of claim 3 wherein said polymer is polyvinyl alcohol andhas a viscosity of 15-200 centipoises.

References Cited UNITED STATES PATENTS 2,743,194 4/1956 Berner et al1l7139.5

WILLIAM D. MARTIN, Primary Examiner T. G. DAVIS, Assistant Examiner US.Cl. X.R. 117161

